KR101725996B1 - White heat-curable silicone/epoxy hybrid resin composition for optoelectronic use, making method, premolded package, and led device - Google Patents

Abstract

(R¹, R²는 동일하거나 상이한 탄소수 6 이상의 유기기이다)
본 발명의 백색 열경화성 실리콘 에폭시 혼성 수지 조성물은 경화성이 우수하고, 양호한 강도를 가짐과 동시에, 장기간에 걸쳐 내열성, 내광성을 유지하여, 균일하고 황변이 적은 경화물을 제공한다.(A) a thermosetting silicone resin, (B) a triazine derivative epoxy resin composition, (C) a white pigment, (D) an inorganic filler (except for a white pigment), (E) a curing accelerator, Wherein the antioxidant of the component (F) is a phosphite compound represented by the general formula (1), and the mixing ratio of the component (A) to the component (B) is 5:95 to 95: And a thermosetting silicone epoxy resin composition for forming a thermosetting silicone epoxy resin.
≪ Formula 1 >

(R ¹ and R ² are the same or different organic groups having 6 or more carbon atoms)
The white thermosetting silicone epoxy hybrid resin composition of the present invention is excellent in curability, has good strength and maintains heat resistance and light resistance for a long period of time and provides a uniform and less yellowish cured product.

Description

TECHNICAL FIELD [0001] The present invention relates to a white thermosetting silicone epoxy hybrid composition for forming a photosemiconductor substrate, a method for producing the same, a preformed package and an LED device,

The present invention relates to a white thermosetting silicone epoxy hybrid resin composition for forming a photosemiconductor substrate which maintains whiteness, heat resistance and light fastness and provides a cured product excellent in strength, a process for producing the same, and an LED (Light Emitting Diode and the like, and a LED device.

The optical semiconductor element such as an LED is small and efficiently emits a vivid color. Since it is a semiconductor element, it does not break a bulb, has excellent driving characteristics, and is resistant to repetition of vibration or ON / OFF lighting. Therefore, it is used as various indicators and light sources. As one of substrate materials of optical semiconductor devices using such optical semiconductor elements, polyphthalamide resin (PPA) is widely used today.

However, due to the remarkable progress of the optical semiconductor technology today, the optical semiconductor device is remarkably high-output and short-wavelength. Therefore, in the optical semiconductor device sealing and the substrate using the conventional PPA resin as the uncolored / white material, Deterioration is remarkable, occurrence of color irregularity, peeling, and deterioration of mechanical strength are likely to occur, and it is desired to effectively solve such a problem.

More specifically, Japanese Patent No. 2656336 (Patent Document 1) discloses a B-stage epoxy resin composition for optical semiconductor encapsulation in which the sealing resin comprises an epoxy resin, a curing agent and a curing accelerator, And a cured product of the resin composition which is uniformly mixed with the cured product. It is also described that a bisphenol A type epoxy resin or a bisphenol F type epoxy resin is mainly used as an epoxy resin, and that triglycidyl isocyanate or the like can be used. However, in the examples, triglycidyl isocyanate is added to a small amount of bisphenol A or F type epoxy resin and is used. According to the studies of the present inventors, the epoxy resin composition for optical semiconductor encapsulation on the B- There is a problem of yellowing.

Japanese Patent Application Laid-Open No. 2000-196151 (Patent Document 2), Japanese Patent Application Laid-Open No. 2003-224305 (Patent Document 3), Japanese Patent Application Laid-Open No. 2005-306952 (Patent Document 4) The use of a triazine derivative epoxy resin in an epoxy resin composition for sealing a device has been described, but all of them are not sufficient to solve the problem of yellowing due to high temperatures and long time left to stand.

Japanese Patent Application Laid-Open No. 2006-77234 (Patent Document 5) discloses a resin composition for encapsulating an LED element containing an organopolysiloxane having a weight average molecular weight of 5 10 ³ or more and a condensation catalyst. However, this organopolysiloxane is not suitable for transfer molding or compression molding because it must be liquid at room temperature having transparency.

Japanese Patent No. 2656336 Japanese Patent Application Laid-Open No. 2000-196151 Japanese Patent Application Laid-Open No. 2003-224305 Japanese Patent Application Laid-Open No. 2005-306952 Japanese Patent Application Laid-Open No. 2006-77234

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a cured product which is a hybrid material of a silicone resin and an epoxy resin and which improves the strength of the silicone resin, maintains heat resistance and light resistance for a long period of time, It is an object of the present invention to provide a white thermosetting silicone epoxy hybrid resin composition for forming a semiconductor substrate, a process for producing the same, and a preformed package such as an LED and the like molded with a cured product of the composition and an LED device.

The present inventors have intensively studied in order to achieve the above object and as a result have found that the use of a thermosetting silicone resin, a triazine derivative epoxy resin composition, a white pigment, an inorganic filler (except for a white pigment), a curing accelerator and a specific antioxidant It has been found that a white thermosetting silicone epoxy hybrid resin composition for forming a semiconductor substrate can be a cured product having excellent curability, heat resistance, light resistance and good strength, and has completed the present invention.

Accordingly, the present invention provides the following white thermosetting silicone epoxy hybrid resin composition for forming a photosemiconductor substrate, a method of producing the same, and a pre-molded package and an LED device having excellent light resistance.

Claim 1:

(A) a thermosetting silicone resin, (B) a triazine derivative epoxy resin composition, (C) a white pigment, (D) an inorganic filler (except for a white pigment), (E) a curing accelerator, , Wherein the antioxidant of the component (F) is a phosphite compound represented by the following formula (1), and the mixing ratio of the component (A) to the component (B) is from 5:95 to 95: 5 A white thermosetting silicone epoxy hybrid resin composition for forming a semiconductor substrate.

(Wherein R ¹ and R ² are the same or different organic groups having 6 or more carbon atoms)

Claim 2:

The white thermosetting silicone epoxy hybrid resin composition according to claim 1, wherein any one or both of R ¹ and R ² is an alkyl group having 6 or more carbon atoms as the antioxidant of the component (F).

[Claim 3]

The white thermosetting silicone epoxy hybrid resin composition according to claim 1 or 2, wherein the thermosetting silicone resin of component (A) is represented by the following average composition formula (2).

≪ Average composition formula 2 &

(Wherein, R ³ is the same or a different organic group having 1 to 20, R ⁴ represents an organic group of the same or different C 1 -C 4, 0.8≤a≤1.5, 0≤b≤0.3, 0.001≤c≤ 0.5, 0.801? A + b + c < 2)

Claim 4:

4. The thermosetting resin composition according to any one of claims 1 to 3, wherein the triazine derivative epoxy resin composition as the component (B) is a thermosetting white resin composition comprising (B-1) a triazine derivative epoxy resin and (B- Silicone epoxy hybrid resin composition.

[Claim 5]

The epoxy resin composition according to any one of claims 1 to 4, wherein the triazine derivative epoxy resin composition (B) is a triazine derivative epoxy resin (B-1) And an equivalent weight of the anhydride group of 0.6 to 2.0, and reacting the resultant mixture with the solid matter to obtain a white thermosetting silicone epoxy hybrid resin composition.

[Claim 6]

6. The white pigment according to any one of claims 1 to 5, wherein the white pigment of component (C) is titanium dioxide having an average particle diameter of 0.05 to 5.0 占 퐉, potassium titanate having an average particle diameter of 0.1 to 3.0 占 퐉, zirconium oxide, , Zinc oxide, alumina, and magnesium oxide,

Wherein the inorganic filler of the component (D) is at least one selected from silica, alumina, magnesium oxide, aluminum hydroxide, zinc oxide, silicon nitride, aluminum nitride and boron nitride each having an average particle size of 4 to 50 탆 White thermosetting silicone epoxy hybrid resin composition.

[Claim 7]

The composition according to any one of claims 1 to 6, wherein the total amount of the inorganic filler of the component (D) and the white pigment of the component (C) is in the range of 50 to 95 mass% (B) is 100 to 1,000 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B), wherein the amount of the white pigment to be incorporated in the composition is 5 to 40% White thermosetting silicone epoxy hybrid resin composition.

Claim 8:

The positive resist composition according to any one of claims 1 to 7, wherein the amount of the curing accelerator (E) is 0.05 to 5% by mass of the whole composition, (F) the amount of the antioxidant is 0.01 to 10% Thermosetting silicone epoxy hybrid resin composition.

Claim 9:

(B) a triazine derivative epoxy resin (B) comprising a pulverized solid obtained by compounding (B-1) a triazine derivative epoxy resin and (B-2) an acid anhydride at an epoxy equivalent / anhydride group equivalent of 0.6 to 2.0, (C) a white pigment, (D) a thermosetting silicone resin, (A) a mixture of components (A) and (B) in a mass ratio of 5:95 to 95: 5, ) Inorganic filler, (E) a curing accelerator, and (F) an antioxidant as a phosphite compound represented by the following formula (1).

&Lt; Formula 1 >

(Wherein R ¹ and R ² are the same or different organic groups having 6 or more carbon atoms)

Claim 10:

(B-1) a triazine derivative epoxy resin and (B-2) an acid anhydride in the presence of a phosphite compound represented by the following formula (1) as an antioxidant (E) (B) a triazine derivative epoxy resin composition comprising a pulverized product of a solid obtained by compounding at a base equivalent of 0.6 to 2.0 and a mixture of the component (E) and / or the component (F) and the thermosetting silicone resin (C) a white pigment, (D) an inorganic filler, and (E) component (B) are mixed in a ratio of 5: 95 to 95: And the component (F) is not used in the reaction, the component is mixed with a component that is not used. The method for producing a white thermosetting silicone epoxy hybrid resin composition for forming a photosemiconductor substrate according to claim 1,

&Lt; Formula 1 >

(Wherein R ¹ and R ² are the same or different organic groups having 6 or more carbon atoms)

Claim 11:

A pre-molded package formed by molding a white thermosetting silicone epoxy hybrid resin composition for forming a photosemiconductor substrate according to any one of claims 1 to 8.

Claim 12:

An LED device assembled using the pre-molded package according to claim 11.

The white thermosetting silicone epoxy hybrid resin composition of the present invention is excellent in curability, has not only good strength, but also maintains heat resistance and light resistance for a long period of time, thereby providing a uniform and less yellowing cured product. Therefore, the pre-mold package formed by the cured product of the composition of the present invention is particularly useful in industry especially for high-luminance LED and solar battery. It is also effective as an underfill material for an LED element.

1 is a cross-sectional view showing an example of a photosemiconductor substrate (LED reflector) using the white thermosetting silicone epoxy hybrid resin composition of the present invention.
2 is a cross-sectional view showing an example of a photocoupler using the white thermosetting silicone epoxy hybrid resin composition of the present invention.

The white thermosetting silicone epoxy hybrid resin composition for forming a photosemiconductor substrate of the present invention contains the following components as essential components.

(A) a thermosetting silicone resin

(B) Triazine derivative epoxy resin composition

(C) a white pigment

(D) Inorganic filler (except for white pigment)

(E) Curing accelerator

(F) Antioxidant

(A) a thermosetting silicone resin

The thermosetting silicone resin of the component (A) according to the present invention is preferably a silanol group-containing organopolysiloxane, particularly a silicone polymer represented by the following formula (2).

(2)

(Wherein, R ³ is the same or a different organic group having 1 to 20, R ⁴ represents an organic group of the same or different C 1 -C 4, 0.8≤a≤1.5, 0≤b≤0.3, 0.001≤c≤ 0.5, 0.801? A + b + c < 2)

Examples of the organic group at R ³ include an unsubstituted or substituted group having 1 to 20 carbon atoms such as an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, A monovalent hydrocarbon group, and the alkyl group is more preferably an alkyl group having 1 to 10 carbon atoms, and may be any of linear, branched and cyclic, and examples thereof include a methyl group, ethyl group, n- Propyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, cyclopentyl group and cyclohexyl group.

The alkenyl group is more preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an aryl group and a propenyl group.

The aryl group is more preferably a C6-C10 aryl group, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

The aralkyl group is more preferably a group having 7 to 10 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylmethyl group.

Further, a substituted monovalent hydrocarbon group in which one or more hydrogen atoms of the unsubstituted monovalent hydrocarbon group are substituted with a halogen atom, cyano group, or the like may be used.

Among them, R ³ in the formula (2) is preferably a methyl group or a phenyl group.

In Formula 2, R ⁴ is the same or different organic group having 1 to 4 carbon atoms, and examples thereof include an alkyl group or an alkenyl group. OR ⁴ represents a portion other than the silanol group (Si-OH) in the terminal groups of the siloxane resin, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group and a butoxy group , A methoxy group and an isopropoxy group which are easily available for raw materials are preferable.

Wherein a, b and c are numbers satisfying 0.8? A? 1.5, 0? B? 0.3, 0.001? C? 0.5, 0.801? A + b + c <2, a? 1.3, 0.001? b? 0.2, 0.01? c? 0.3, and 0.911? a + b + c? 1.8. When the content a of R ³ is less than 0.8, the hardness becomes poor and the anti-cracking property is deteriorated. If it exceeds 1.5, the organic groups are increased to increase the hydrophobicity and soften. Lt; / RTI &gt; If the content b of OR ⁴ exceeds 0.3, the amount of terminal groups increases and the molecular weight tends to be small, so that the crack preventing performance is not exhibited. When the content c of OH is more than 0.5, the proportion involved in the condensation reaction at the time of heat curing becomes high, and crack resistance becomes poor although it is high in hardness. If c is less than 0.001, the melting point tends to be high, and there is a problem in workability. As a condition for controlling the c, the complete condensation ratio of the alkoxy group is preferably 86 to 96%, and when it is less than 86%, the melting point is lowered. When it exceeds 96%, the melting point tends to become too high.

The component (A) of the above-mentioned formula (2) is generally a Q unit derived from a tetrafunctional silane [SiO _4/2 ], a T unit derived from a trifunctional silane [R ³ SiO _3/2 (R ³ is as defined above, R ³ SiO _2/2 ] derived from a bifunctional silane, and an M unit [R ³ SiO _1/2 ] derived from a monofunctional silane, the component (A) may be represented by the following formula The ratio of the number of moles of T units represented by R ³ SiO _3/2 to the total number of moles of all siloxane units is 70 mol% or more, preferably 75 mol% or more, particularly preferably 80 mol% or more, Mol% or more. If the T unit is less than 70 mol%, the overall balance of hardness, adhesion, overview and the like may be disrupted. The balance may be an M, D or Q unit, and the sum thereof is preferably 30 mol% or less. With respect to the melting point, the higher the Q and T units, the higher the melting point, and the higher the D and M units, the lower the melting point. It is more preferable that the ratio of the molar amount of the T unit represented by R ³ SiO _3/2 is 70 mol% or more and the remaining 30 mol% or less is the D unit.

The melting point of the component (A) is 40 to 130 캜, preferably 70 to 80 캜. If the temperature is lower than 40 ° C, the solid phase is not formed, and the solid surface becomes more sticky to make the transfer molding difficult. If the temperature exceeds 130 ° C, the fluidity is lost and transfer molding becomes difficult.

The component (A) can be obtained as a hydrolysis-condensation product of an organosilane represented by the following general formula (3).

(Wherein, R ³ is as defined above. X is a halogen atom or an alkoxy group, especially an alkoxy group having 1 to 4 carbon atoms such as chlorine, n is 1, 2 or 3)

In this case, X is preferably a halogen atom, particularly a chlorine atom, from the viewpoint of obtaining a solid organopolysiloxane.

In the above formula (3), n represents an integer of 1 to 3. when n is 2 or 3, that is, if there is a plurality of R ^3, each R ³ may be the same or different from each other. n is preferably n = 1 in that a solid polysiloxane can be obtained.

Examples of the silane compound represented by the general formula (3) include methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, methylvinyldichlorosilane, vinyl trichlorosilane, diphenyldichlorosilane, methyltrimethoxysilane, Organotrichlorosilanes such as methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, and phenyltriethoxysilane, and organotrialkoxysilanes; And diorganoalkoxysilane such as dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylvinyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, and the like. It is particularly preferable to use methyltrichlorosilane. It is also effective to use phenyltrichlorosilane in combination.

The amount of trichlorosilane or trialkoxysilane to be used is preferably selected from the viewpoint of obtaining a silanol group-containing organopolysiloxane containing 70 mol% or more of T units.

The hydrolysis and condensation of the silane compound having a hydrolysable group may be carried out by a conventional method. For example, an acid catalyst such as acetic acid, hydrochloric acid, or sulfuric acid, or an alkali such as sodium hydroxide, potassium hydroxide or tetramethylammonium hydroxide It is preferably carried out in the presence of a catalyst. For example, when a silane containing a chlorine group is used as the hydrolyzable group, a desired hydrolysis condensate having a desired molecular weight can be obtained using hydrochloric acid generated by hydrogenation as a catalyst.

The amount of water to be added at the time of hydrolysis and condensation is usually 0.9 to 1.6 mol, preferably 1.0 to 1.3 mol, per mol of the total amount of the hydrolyzable group (for example, a chlorine group) in the silane compound having the hydrolysable group to be. When the added amount satisfies the range of 0.9 to 1.6 moles, the composition described later is excellent in workability and the cured product thereof is excellent in toughness.

The silane compound having a hydrolysable group is preferably hydrolyzed and used in an organic solvent such as an alcohol, a ketone, an ester, a cellosolve or an aromatic compound. Specific examples thereof include alcohols such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, n-butanol and 2-butanol, and aromatic compounds such as toluene and xylene. The curing property of the composition and the toughness , It is more preferable to use isopropyl alcohol or a combination of toluene.

In this case, the reaction temperature for the hydrolysis and condensation is preferably 10 to 120 캜, more preferably 20 to 100 캜. When the reaction temperature satisfies this range, a hydrolysis-condensation product of a solid which can be used in the subsequent step is obtained without gelation.

When methyltrichlorosilane is used as a specific synthesis method, water and isopropyl alcohol are added to methyltrichlorosilane dissolved in toluene to partially hydrolyze (reaction temperature is -5 to 100 ° C), and then the remaining chlorine group And a solid silicone polymer having a melting point of 76 캜 is obtained by adding water for hydrolyzing the whole amount and reacting.

Thus, an aimed organopolysiloxane is obtained. The melting point of the organopolysiloxane is 50 to 100 캜, preferably 70 to 80 캜. When the temperature is lower than 50 DEG C and higher than 100 DEG C, there is a problem that kneading becomes difficult due to the mixing workability of subsequent steps.

(B) Triazine derivative epoxy resin composition

The triazine derivative epoxy resin composition used in the present invention preferably contains the following (B-1) triazine derivative epoxy resin and (B-2) acid anhydride.

(B-1) triazine derivative epoxy resin

The triazine derived epoxy resin used in the present invention is preferably a 1,3,5-triazine nucleus derivative epoxy resin. Especially, an epoxy resin having an isocyanurate ring is preferable because it has excellent light resistance and electrical insulation, and has two epoxy groups, more preferably three epoxy groups, per one isocyanurate ring. Specifically, tris (2,3-epoxypropyl) isocyanurate, tris (? -Methyl glycidyl) isocyanurate, tris (? - methylglycidyl) isocyanurate and the like can be used .

The softening point of the triazine derived epoxy resin used in the present invention is preferably 90 to 125 캜. In the present invention, the triazine derivative epoxy resin does not include hydrogenated triazine rings.

If necessary, epoxy resins other than those described above may be used in a certain amount within the range not to impair the effects of the present invention, preferably 30 parts by mass or less, particularly 10 parts by mass or less based on 100 parts by mass of the triazine derivative epoxy resin . Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, 3,3 ', 5,5'-tetramethyl-4,4'-biphenol type epoxy resin or 4,4'-biphenol Phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, naphthalene diol type epoxy resin, trisphenylol methane type epoxy resin, tetrakisphenyl An epoxy resin obtained by hydrogenating an aromatic ring of an all ethane-type epoxy resin and a phenol dicyclopentadiene novolak-type epoxy resin, and an alicyclic epoxy resin. Of these epoxy resins, epoxy resins obtained by hydrogenating aromatic rings from heat resistance and ultraviolet ray resistance and alicyclic epoxy resins are preferred. The other epoxy resin preferably has a softening point of 70 to 100 캜.

(B-2) acid anhydride

The acid anhydride of the component (B-2) used in the present invention acts as a curing agent and is preferably non-aromatic in order to provide light resistance and does not have a carbon-carbon double bond. Examples thereof include hexahydrophthalic anhydride Methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride and hydrogenated methylnadonic anhydride, among which methylhexahydrophthalic anhydride is preferable. These acid anhydride-based curing agents may be used singly or in combination of two or more kinds.

The compounding amount of the acid anhydride-based curing agent is 0.6 to 2.0 equivalents, preferably 1.0 to 2.0 equivalents, more preferably 1.2 to 1.6 equivalents, of the acid anhydride group per one equivalent of the epoxy group of the above-mentioned triazine derivative epoxy resin. If the amount is less than 0.6 equivalents, the curing defects may occur and the reliability may be lowered. If the amount is more than 2.0 equivalents, the unreacted curing agent remains in the cured product to deteriorate the moisture resistance of the obtained cured product.

In the present invention, the triazine-derivative epoxy resin (B-1) and the acid anhydride (B-2) are mixed in an equivalent weight of epoxy group / acid anhydride group of 0.6 to 2.0, more preferably 1.2 to 1.6, In the presence of (F) an antioxidant and / or (E) a curing accelerator may be used as the resin component. If the amount is less than 0.6 equivalents, the curing defects may occur and the reliability may be lowered. If the amount is more than 2.0 equivalents, the unreacted curing agent remains in the cured product to deteriorate the moisture resistance of the obtained cured product. As the curable resin composition, it is preferable to use the solid material because it can be used as a solid thermosetting resin having good workability.

As the detailed reaction condition, the antioxidant of the component (F) is added to the components (B-1) and (B-2), preferably the components (B-1) (B-1) to the component (B-2) at 120 to 120 ° C., preferably 80 to 110 ° C. for 4 to 20 hours, preferably 6 to 15 hours, Or the components (F) and (E) are added to the components (B-1) and (B-2) and the mixture is preliminarily heated at 30 to 80 ° C, preferably 40 to 60 ° C for 10 to 72 hours, For 60 hours to obtain a solid having a softening point of 50 to 100 占 폚, preferably 60 to 90 占 폚, and pulverizing and mixing the resultant mixture. When the softening point of the substance obtained by the reaction is less than 50 캜, it does not become a solid, and when the temperature exceeds 100 캜, the fluidity may decrease.

The solid [component (B)] is exemplified by a compound represented by the following formula (4).

(Wherein R is an acid anhydride residue and m is a number of 0 to 200)

(A) / (B) of the thermosetting silicone resin as the component (A) and the triazine derivative epoxy resin composition as the component (B) is preferably in the range of 5 parts by mass / 95 parts by mass to 95 parts by mass / 5 parts by mass . When the amount of the component (A) / (B) is less than 5 parts by mass / 95 parts by mass, the weatherability becomes insufficient, and when exceeding 95 parts by mass / 5 parts by mass, the strength is insufficient and the reliability of the preformed package becomes insufficient. More preferably, (A) / (B) is in a range of 10 parts by mass / 90 parts by mass to 90 parts by mass / 10 parts by mass, more preferably 20 parts by mass / 80 parts by mass and 80 parts by mass / 20 parts by mass.

(C) a white pigment

The white pigment of the component (C) according to the present invention is added to enhance whiteness as a white colorant. In particular, when the composition of the present invention is used in a preformed package for an LED, titanium dioxide is used as a white colorant . The unit lattice of the titanium dioxide is not related to either the rutile type or the anatase type. In addition, the average particle size and shape are not limited, but it is preferable to be a derivative in order to increase whiteness with a small amount. The titanium dioxide is preferably a rutile type surface treated in advance with a hydrous oxide such as Al or Si, silane or the like in order to improve the compatibility with the resin or the inorganic filler, the dispersibility and the light resistance.

The average particle diameter and shape are not limited, but the average particle diameter is usually 0.05 to 5.0 mu m, preferably 0.1 to 3.0 mu m, more preferably 0.1 to 1.0 mu m.

The average particle size can be obtained as a mass average value D ₅₀ (or median diameter) in the particle size distribution measurement by the laser diffraction method.

As the white pigment (white colorant), potassium titanate, zirconium oxide, zinc sulfide, zinc oxide, alumina, magnesium oxide and the like having an average particle size of 0.05 to 5.0 mu m, particularly 0.1 to 3.0 mu m, Can also be used in combination.

The amount of the white pigment to be added is preferably 3 to 200 parts by mass, particularly 5 to 150 parts by mass, particularly preferably 10 to 120 parts by mass, based on 100 parts by mass of the component (A), more preferably 5 to 40% by mass, 30% by mass is preferable. If it is less than 5% by mass, sufficient whiteness may not be obtained. If it is more than 40% by mass, the fluidity may be lowered and problems may occur in the formability, resulting in uncharged or voids.

(D) Inorganic filler

As the inorganic filler of the component (D) to be blended in the white thermosetting silicone epoxy hybrid resin composition of the present invention, those blended in an epoxy resin composition or a silicone resin composition can be used, but the white pigment (C) is excluded. Examples of the filler include silica such as fused silica and crystalline silica, fibrous fillers such as alumina, magnesium oxide, aluminum hydroxide, zinc oxide, silicon nitride, aluminum nitride, boron nitride, glass fibers and wollastonite, And the like. These inorganic fillers may be used singly or in combination of two or more kinds.

In the present invention, particularly, fused silica and fused spherical silica are preferably used, and the particle size thereof is not particularly limited, but an average particle diameter is preferably 4 to 50 μm, more preferably 7 to 45 μm in view of moldability and fluidity. In addition, in order to obtain high fluidity, it is preferable to use a material having an average particle diameter of 4 to 50 mu m in combination with a fine region of 3 mu m or less, a medium-diameter region of 4 to 8 mu m, and a rough region of 10 to 50 mu m desirable. In the case of molding a preformed package having a shoulder or as an underfill material, it is preferable to use an inorganic filler having an average particle diameter of 1/2 of the thickness of the shoulder.

The inorganic filler may be blended with a surface-treated with a coupling agent such as a silane coupling agent or a titanate coupling agent in order to strengthen the bonding strength between the resin and the inorganic filler.

Examples of such a coupling agent include epoxy compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Amino functional alkoxysilanes such as functional alkoxysilanes, N-β (aminoethyl) - γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane , mercapto functional alkoxysilane such as? -mercaptopropyltrimethoxysilane, and the like. The amount of the coupling agent used in the surface treatment and the surface treatment method are not particularly limited.

The amount of the inorganic filler to be filled is preferably 100 to 1,000 parts by mass, particularly preferably 200 to 900 parts by mass based on 100 parts by mass of the total amount of (A) the thermosetting silicone resin and (B) the triazine derivative epoxy resin composition. If the amount is less than 100 parts by mass, sufficient strength may not be obtained. If the amount is more than 1,000 parts by mass, defective filling or flexibility due to thickening may be lost, resulting in peeling or the like in the element. The inorganic filler is preferably contained in an amount of 45 to 90% by mass, more preferably 50 to 90% by mass, of the entire composition. The total amount of the component (C) and the component (D) is preferably from 50 to 95 mass% of the entire composition.

(E) Curing accelerator

As the curing accelerator for the component (E), those known as curing accelerators for the epoxy resin composition can be used, and although not particularly limited, tertiary amines, imidazoles, organic carboxylic acid salts thereof, organic carboxylic acid Phosphorus-based curing catalysts such as metal salts, metal-organic chelate compounds, aromatic sulfonium salts, organic phosphine compounds and phosphonium compounds, and salts thereof. Among them, imidazoles, phosphorus-based curing catalysts such as 2-ethyl-4-methylimidazole or methyl-tributylphosphonium-dimethylphosphate and quaternary phosphonium bromide are more preferable.

The curing accelerator is preferably used in an amount of 0.05 to 5% by mass, particularly 0.1 to 2% by mass, based on the entire composition. Outside of the above range, the balance between heat resistance and moisture resistance of the cured product of the composition may deteriorate.

(F) Antioxidant

As the antioxidant of the component (F) used in the white thermosetting silicone epoxy hybrid resin composition of the present invention, a phosphorus-based antioxidant is used in view of maintaining long-term heat resistance and weather resistance at a high temperature.

As the phosphorus-containing antioxidant, those represented by the following general formula (1) are used.

&Lt; Formula 1 >

(Wherein R ¹ and R ² are the same or different organic groups having 6 or more carbon atoms and particularly preferably an alkyl group having 6 to 20 carbon atoms, particularly 8 to 16 carbon atoms and an aryl group having 6 to 20 carbon atoms, It is preferable that either one or both of R ¹ and R ² is an alkyl group)

Examples of the phosphorus antioxidant include trioctyl phosphite, dioctyl monodecyl phosphite, didecyl mono octyl phosphite, tridecyl phosphite, diphenyl monooctyl phosphite, diphenyl monodecyl phosphite, di (p-cresyl) Mono (tridecyl) phosphite, tris (2-ethylhexyl) phosphite, diphenylmono (tridecyl) phosphite and the like. Among them, tridecyl phosphite is preferable.

The blending amount of the antioxidant is preferably 0.01 to 10% by mass, particularly 0.03 to 5% by mass, based on the whole composition. If the blending amount is too small, sufficient heat resistance can not be obtained and discoloration may occur. When the blending amount is excessively large, curing hindrance may occur and sufficient curability and strength may not be obtained.

(G) Other additives

The white thermosetting silicone epoxy hybrid resin composition of the present invention may further contain various additives such as the following curing catalyst for silicone resin, if necessary.

Curing catalyst

The curing catalyst according to the present invention is a condensation curing catalyst for curing a thermosetting silicone resin. Examples of the condensation curing catalyst include basic compounds such as trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide, n-hexylamine, tributylamine, diazabicyclo-undecene (DBU) and dicyandiamide ; Tetrabutyl titanate, tetrabutyl titanate, titanium acetylacetonate, aluminum triisobutoxide, aluminum triisopropoxide, zirconium tetra (acetylacetonate), zirconium tetrabutyrate, cobalt octylate, cobalt acetylacetonate, Metal-containing compounds such as iron acetylacetonate, tin acetylacetonate, dibutyltin octylate and dibutyltin laurate, aluminum trisacetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, diisopropoxybis (Ethyl acetoacetate) titanium, diisopropoxybis (ethylacetoacetate) titanium, and the like. Of these, zinc octylate, zinc benzoate, zinc p-tert-butylbenzoate, zinc laurate, zinc stearate and aluminum triisopropoxide are particularly preferable. Among them, zinc benzoate and an organic titanium chelate compound are preferably used.

In order to harden the epoxy resin composition and the silicone resin substantially at the same time, these catalysts and (E) curing accelerator may be used in combination or, in some cases, both compositions may be cured with one type of catalyst.

The blending amount of the curing catalyst is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 6 parts by mass based on 100 parts by mass of the component (A).

If necessary, an epoxy resin other than the above may be used together with a certain amount or less within the range not to impair the effect of the present invention. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, 3,3 ', 5,5'-tetramethyl-4,4'-biphenol type epoxy resin or 4,4'-biphenol Phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, naphthalene diol type epoxy resin, trisphenylol methane type epoxy resin, tetrakisphenyl An epoxy resin obtained by hydrogenating an aromatic ring of an olefin type epoxy resin and a phenol dicyclopentadiene novolak type epoxy resin, and the like. The other epoxy resin preferably has a softening point of 70 to 100 캜.

In addition, additives such as various thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers, silicone-based low stress agents, waxes, silane or titanium-based coupling agents, and halogen trap agents may be added for the purpose of improving the properties of the resin It can be added and added in a range that does not impair the effect of the present invention.

The reflectance at 380 to 750 nm of the cured product obtained by curing the silicone epoxy hybrid resin composition containing the essential components (A) to (F) of the present invention was 70% or more as an initial value, and after deterioration test at 180 占 폚 for 24 hours It is preferable that the reflectance is 70% or more. If the reflectance is less than 70%, there arises a problem that the use period for the semiconductor element case for LEDs is shortened in use.

When the composition of the present invention is used for sealing a usual semiconductor sealing material or various modules for vehicle mounting, carbon black or the like is used as a coloring agent. As the carbon black, any commercially available carbon black can be used, but preferably it is preferable that the carbon black contains a large amount of an alkali metal or a halogen and a good purity.

As the method for producing the composition of the present invention, a silicone resin, an epoxy resin, a curing agent, a curing catalyst, a filler, and other additives are compounded in a predetermined composition ratio and sufficiently uniformly mixed by a mixer or the like, Truing and the like, followed by cooling and solidifying and pulverizing to an appropriate size to obtain a molding material for an epoxy resin composition.

The silicone epoxy hybrid resin composition of the present invention thus obtained is excellent in moldability, heat resistance and light fastness, particularly excellent in ultraviolet ray resistance, and therefore is preferable not only for white and blue, but also for preformed packages for ultraviolet LEDs, .

Also included in the scope of the present invention is a matrix-type metal substrate or an organic substrate on which a lead portion or a pad portion is formed, in which only the LED element mounting portion is not occupied and the package is sealed with this material.

It can also be used for sealing of ordinary semiconductor sealing materials and various modules for vehicle mounting.

Here, FIG. 1 shows a cross-sectional view of an LED reflector, which is an example of a semiconductor device using a white thermosetting silicone epoxy hybrid resin composition for forming a photosemiconductor substrate of the present invention. In the LED shown in Fig. 1, a semiconductor element 1 made of a compound semiconductor is die-bonded to a lead frame 2a and further wire-bonded to a separate lead frame 2b by a bonding wire 3. These elements are covered with a transparent sealing resin 4. The semiconductor element covered with the sealing resin 4 is held by a cured product (optical semiconductor case 5 as a white reflector) of the white thermosetting silicone epoxy hybrid resin composition for forming an optical semiconductor substrate of the present invention ). (6) is a lens.

Fig. 2 shows a sectional view of a photocoupler which is an example of a semiconductor device using the composition of the present invention. 2, a semiconductor element 11 made of a compound semiconductor is die-bonded to a lead frame 12 and further bonded to a separate lead frame (not shown) by a bonding wire 13, . The semiconductor element 14 for light reception is die-bonded on the lead frame 15 so as to face the semiconductor element 11 and further bonded to a separate lead frame (not shown) by the bonding wire 16 It is wire-bonded. These semiconductor elements are filled with the transparent sealing resin 17. The semiconductor element covered with the sealing resin 17 is resin-sealed with the white thermosetting silicone epoxy resin composition 18 of the present invention.

In this case, the most common method for sealing the white thermosetting silicone epoxy hybrid resin composition of the present invention is a low pressure transfer molding method. The molding temperature of the silicone epoxy hybrid resin composition of the present invention is preferably from 150 to 185 DEG C for 30 to 180 seconds. Post curing may be performed at 150 to 185 캜 for 2 to 20 hours.

<Examples>

Hereinafter, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.

The raw materials used are shown below.

(A) a thermosetting silicone resin

[Synthesis Example 1]

100 parts by mass of methyltrichlorosilane and 200 parts by mass of toluene were placed in a 1 liter flask, and a mixture of 8 parts by mass of water and 60 parts by mass of isopropyl alcohol was added dropwise in an ice bath. The inner temperature was dropped from -5 to 0 占 폚 over 5 to 20 hours, and then the mixture was heated and stirred at a reflux temperature for 20 minutes. The mixture was cooled to room temperature, and 12 parts by mass of water was added dropwise at 30 DEG C or lower for 30 minutes, followed by stirring for 20 minutes. Further, 25 parts by mass of water was added dropwise, followed by stirring at 40 to 45 ° C for 60 minutes. Then, 200 parts by mass of water was added to separate the organic layer. The organic layer was washed with water until neutral, and then subjected to azeotropic dehydration, filtration and vacuum stripping to obtain 36.0 parts by mass of a thermosetting silicone resin (A-1) represented by the following formula 5 as a colorless transparent solid .

[Synthesis Example 2]

80 parts by mass of methyltrichlorosilane, 20 parts by mass of tetraethoxysilane and 200 parts by mass of toluene were placed in a 1 liter flask, and a mixed solution of 8 parts by mass of water and 60 parts by mass of isopropyl alcohol was added dropwise in an ice bath. The inner temperature was dropped from -5 to 0 占 폚 over 5 to 20 hours, and then the mixture was heated and stirred at a reflux temperature for 20 minutes. The mixture was cooled to room temperature, and 12 parts by mass of water was added dropwise at 30 DEG C or lower for 30 minutes, followed by stirring for 20 minutes. Further, 25 parts by mass of water was added dropwise, followed by stirring at 40 to 45 ° C for 60 minutes. Then, 200 parts by mass of water was added to separate the organic layer. The organic layer was washed with water until neutral, and then subjected to azeotropic dehydration, filtration and vacuum stripping to obtain 36.0 parts by mass of a thermosetting silicone resin (A-2) represented by the following formula 6 as a colorless transparent solid .

(B-1) triazine derivative epoxy resin

Tris (2,3-epoxypropyl) isocyanate (TEPIC-S: trade name, epoxy equivalent weight 100, manufactured by Nissan Chemical Industries, Ltd.)

(B-2) acid anhydride

Non-carbon-carbon double bond acid anhydrides; Methylhexahydrophthalic anhydride (Ricaside MH: trade name, manufactured by Shin-Nippon Chemical Co., Ltd.)

Carbon-containing double bond acid anhydrides; Tetrahydrophthalic anhydride (ricaside TH: trade name, manufactured by Shin-Nippon Chemical Co., Ltd.)

(C) a white pigment

Titanium dioxide: Rutile type R-45M

            (Trade name: average particle diameter 0.29 mu m, manufactured by Sakai Chemical Industry Co., Ltd.)

(D) Inorganic filler

Molten spherical silica: MSR-4500TN

                  (Average particle diameter: 45 mu m, trade name, manufactured by Ryomori Co., Ltd.)

(E) Curing accelerator

Phosphorus cure catalyst: methyl-tributylphosphonium-dimethyl phosphate

                (PX-4MP: trade name, manufactured by NIPPON KAGAKU KOGYO CO., LTD.)

(F) Antioxidant

(F-1) tridecyl phosphite

      (Adekastab 3010: trade name of ADEKA)

(F-2) triphenylphosphine

(G) Other additives

(i) condensation curing catalyst

Curing catalyst for silicone resin: zinc benzoate (manufactured by Junsei Chemical Co., Ltd.)

(ii)

Calcium stearate (manufactured by Wako Pure Chemical Industries, Ltd.)

[Synthesis Example 3] Preparation of epoxy resin prepolymer

Various components were compounded in the ratios shown in Table 1 below and heated under predetermined reaction conditions to react the epoxy resin with the acid anhydride.

[Examples 1 to 3, Comparative Examples 1 to 3]

Various components were mixed in the ratios shown in Table 2 below, uniformly mixed, and then kneaded with a heat biaxial roll to obtain a white silicone epoxy hybrid resin composition.

With respect to the obtained composition, various physical properties were measured by the following measurement methods. The results are shown in Table 2. All molding was performed with a transfer molding machine.

"Spiral flow value"

Using a mold conforming to the EMMI standard, at 175 DEG C, 6.9 N / mm &lt; 2 &gt; and a molding time of 120 seconds.

"Melt viscosity"

Using a flow rate flow tester, a nozzle having an inner diameter of 1 mm was used under a pressure of 25 kgf, and the viscosity was measured at a temperature of 175 ° C.

"Bending strength"

Using a mold conforming to the EMMI standard, at 175 DEG C, 6.9 N / mm &lt; 2 &gt; and a molding time of 120 seconds.

&Quot; Light reflectance &quot;

(Cured product) having a diameter of 50 mm and a thickness of 3 mm was molded under conditions of 175 ° C, 6.9 N / mm 2 and a molding time of 90 seconds. (High-pressure mercury lamp of 60 mW / cm) 24 hours later, the optical reflectance at a wavelength of 450 nm was measured using X-rite 8200 manufactured by SDG Corporation.

According to Examples 1 to 3 in Table 2, it is possible to obtain a white thermosetting silicone epoxy hybrid resin composition which is allowed to stand at 180 占 폚 for 24 hours and provides a cured product having a high light reflectance even after 24 hours of UV irradiation. Therefore, it has been confirmed that a semiconductor device in which a reflector for an LED is sealed as a cured product of the composition is useful.

1, 11, 14: Semiconductor device
2: Lead frame (Ag plated Cu frame or NiPdAu plated Cu frame)
3, 13, 16: bonding wire
4, 17: Transparent sealing resin
5: White reflector (cured product of white thermosetting silicone epoxy hybrid resin composition)
6: Lens
12, 15: Lead frame
18: A cured product of a white thermosetting silicone epoxy hybrid resin composition

Claims (12)

(A) a thermosetting silicone resin, (B) a triazine derivative epoxy resin composition, (C) a white pigment, (D) an inorganic filler (except for a white pigment) (B-1) a triazine derivative epoxy resin and (B-2) an acid anhydride, wherein the triazine derivative epoxy resin composition comprises (B-1) Wherein the antioxidant of the component (E) is at least one compound selected from the group consisting of compounds represented by the following formulas (1), (2) and (3) (A) and the component (B) is in a mass ratio of 5:95 to 95: 5, the amount of the component (D) is less than 100 parts by mass (E) is contained in an amount of from 0.01 to 10 parts by weight based on 100 parts by weight of the whole composition, % By weight of the white heat-curable silicone for the optical semiconductor device according to claim epoxy hybrid resin composition.
&Lt; Average composition formula 2 &

(Wherein, R ³ is the same or a different organic group having 1 to 20, R ⁴ represents an organic group of the same or different C 1 -C 4, 0.8≤a≤1.5, 0≤b≤0.3, 0.001≤c≤ 0.5, 0.801? A + b + c < 2)
&Lt; Formula 1 >

(Wherein R ¹ and R ² are the same or different and each is an alkyl group having 6 to 20 carbon atoms) The white pigment according to claim 1, wherein the white pigment of component (C) is titanium dioxide having an average particle size of 0.05 to 5.0 탆, potassium titanate having an average particle size of 0.1 to 3.0 탆, zirconium oxide, zinc sulfide, zinc oxide, And at least one kind selected from the group consisting of
Wherein the inorganic filler of the component (D) is at least one selected from silica, alumina, magnesium oxide, aluminum hydroxide, zinc oxide, silicon nitride, aluminum nitride and boron nitride each having an average particle size of 4 to 50 탆 White thermosetting silicone epoxy hybrid resin composition. The composition according to claim 1, wherein the total amount of the inorganic filler of the component (D) and the white pigment of the component (C) is in the range of 50 to 95 mass% of the total composition, and the amount of the white pigment of the component (C) Of the total weight of the white thermosetting silicone epoxy hybrid resin composition. The white thermosetting silicone epoxy hybrid resin composition according to any one of claims 1 to 3, further comprising (F) a curing accelerator in an amount of 0.05 to 5 mass% of the entire composition. (B) a triazine derivative epoxy resin (B) comprising a pulverized solid obtained by compounding (B-1) a triazine derivative epoxy resin and (B-2) an acid anhydride in an epoxy equivalent / anhydride group equivalent of 0.6 to 2.0, (A) and a thermosetting silicone resin represented by the following average composition formula (2), wherein the mixing ratio of the component (A) to the component (B) is from 5:95 to 95: 5 (C) a white pigment, (D) 100 to 1,000 parts by mass of the inorganic filler per 100 parts by mass of the total amount of the components (A) and (B), and (E) 0.01 to 10% by mass Is mixed with a phosphite compound represented by the following formula (1): < EMI ID = 1.0 >
&Lt; Average composition formula 2 &

(Wherein, R ³ is the same or a different organic group having 1 to 20, R ⁴ represents an organic group of the same or different C 1 -C 4, 0.8≤a≤1.5, 0≤b≤0.3, 0.001≤c≤ 0.5, 0.801? A + b + c &lt; 2)
&Lt; Formula 1 &gt;

(Wherein R ¹ and R ² are the same or different and each is an alkyl group having 6 to 20 carbon atoms) (B-1) a triazine derivative epoxy resin and (B-2) acid anhydride in the presence of a phosphite compound represented by the following formula (1) in an amount of 0.01 to 10 mass% (A) a thermosetting silicone resin (A) represented by the following average compositional formula (2), and (B) a mixture of a triazine derivative epoxy resin composition (B) containing a ground product of a solid obtained by mixing and reacting (A), (B), and (C) the white pigment and (D) the inorganic filler in an amount of from 5:95 to 95: (B) is 100 to 1,000 parts by mass based on 100 parts by mass of the total amount of the component (B).
&Lt; Formula 1 >

(Wherein R ¹ and R ² are the same or different and each is an alkyl group having 6 to 20 carbon atoms)
&Lt; Average composition formula 2 &

(Wherein, R ³ is the same or a different organic group having 1 to 20, R ⁴ represents an organic group of the same or different C 1 -C 4, 0.8≤a≤1.5, 0≤b≤0.3, 0.001≤c≤ 0.5, 0.801? A + b + c < 2) 7. The process according to claim 5 or 6, further comprising (F) a curing accelerator. (B) a triazine derivative epoxy resin (B) in the presence of 0.01 to 10 mass% of a total amount of the composition as a curing accelerator (F) or a curing accelerator (F) as an antioxidant in the presence of a phosphite compound represented by the following formula (B) a triazine derivative epoxy resin composition comprising (B) a crushed solid product obtained by compounding (B-2) an acid anhydride with an epoxy group equivalent / an acid anhydride group equivalent of 0.6 to 2.0, (A) is mixed with the thermosetting silicone resin represented by the following average composition formula (2), wherein the mixing ratio of the component (A) to the component (B) is from 5:95 to 95: 5 100 to 1,000 parts by mass of 100 parts by mass of the total amount of the components (A) and (B), and the component (E) are used in the reaction Is mixed with the component (E) The method of manufacturing an optical semiconductor device, the white heat-curable silicone epoxy hybrid resin composition.
&Lt; Formula 1 >

(Wherein R ¹ and R ² are the same or different and each is an alkyl group having 6 to 20 carbon atoms)
&Lt; Average composition formula 2 &

(Wherein, R ³ is the same or a different organic group having 1 to 20, R ⁴ represents an organic group of the same or different C 1 -C 4, 0.8≤a≤1.5, 0≤b≤0.3, 0.001≤c≤ 0.5, 0.801? A + b + c < 2) A pre-molded package formed by molding a white thermosetting silicone epoxy hybrid resin composition for optical semiconductor devices according to any one of claims 1 to 3. A LED device assembled using the pre-molded package according to claim 9. delete delete

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